Corrosion found in the Boiler and feed

systems
Corrosion and tube failure caused by water chemistry

Metals obtained from their oxide ores will tend to revert to that state. However , if on
exposure to oxygen the oxide layer is stable , no further oxidation will occur. If it is
porous or unstable then no protection is afforded.

Iron+O2 --- magnetite(stable and protective) + O2----ferrous oxide (porous)

Two principle types of corrosion

Direct chemical-higher temperature metal comes into contact with air or other gasses
(oxidation, Sulphurisation ) Electrochemical-e.g. Galvanic action , hydrogen evolution ,
oxygen absorption

Hydrogen Evolution (low pH attack)

Valency = No of electrons required to fill outer shell

Pure water contains equal amounts of hydrogen and hydroxyl ions . Impurities change the
balance . Acidic water has an excess of hydrogen ions which leads to hydrogen evolution

For hydrogen absorption to occur no oxygen needs to be present, a pH of less than 6.5
and so an excess of free hydrogen ions is required.
The Protective film of hydrogen gas on the cathodic surface breaks down as the hydrogen
combines and bubbles off as diatomic hydrogen gas.

Oxygen Absorption(high O2 corrosion)

pH between 6- 10, Oxygen present. Leads to pitting. Very troublesome and can be due to
ineffective feed treatment prevalent in idle boilers. Once started this type of corrosion
cannot be stopped until the rust scab is removed , either by mechanical means or by acid
cleaning. One special type is called deposit attack, the area under a deposit being
deprived of oxygen become anodic. More common in horizontal than vertical tubing and
often associated with condensers.

Boiler corrosion

General Wastage Common in boilers having an open feed system.

.
.
Pitting -Most serious form of corrosion on the waterside
-Often found in boiler shell at w.l.
-Usually due to poor shape
-In HP blrs found also in screen and generating tubes and
in suphtr tubes after priming.

Corrosion fatigue cracking

Cases found in water tube blrs where due to alternating cyclic stresses set up in tube
material leading to a series of fine cracks in wall. Corrosive environment aggravates.
Trans crystalline

more in depth: Occurs in any location where cyclic stressing of sufficient magnitude are
present

Rapid start up and shut down can greatly increase susceptibility.

Common in wall and supht tubes, end of the membrane on waterwall tubes, economisers,
deaerators . Also common on areas of rigid constraint such as connections to inlet and
outlet headers

Other possible locations and causes are in grooves along partially full boiler tubes (cracks
normally lie at right angle to groove ), at points of intermittent stm blanketing within
generating tubes, at oxygen pits in waterline or feed water lines, in welds at slag pockets
or points of incomplete fusion , in sootblower lines where vibration stresses are
developed , and in blowdown lines.

Caustic cracking (embrittlement) or stress corrosion cracking

Pure iron grains bound by cementite ( iron carbide).

Occurs when a specific corrodent and sufficient tensile stress exists

Due to improved water treatment caustic stress- Corrosion cracking ( or caustic

embrittlement ) has all but been eliminated.

It can however be found in water tubes , suphtr and reheat tubes and in stressed
components of the water drum.
The required stress may be applied ( e.g. thermal, bending etc. ) or residual ( e.g.
welding)
Boiler steel is sensitive to Na OH , stainless steel is sensitive to NaOH and chlorides
A large scale attack on the material is not normal and indeed uncommon. The
combination of NaOH , some soluble silica and a tensile stress is all that is required to
form the characteristic intergranular cracks in carbon steel.

Concentrations of the corrodent may build up in a similar way to those caustic

corrosion i.e.

 DNB
 Deposition
 Evaporation at water line
 And also by small leakage

Caustic corrosion at temperatures less than 149oC are rare

NaOH concentration may be as low as 5% but increased susceptibility occurs in the range
20- 40 %
Failure is of the thick walled type regardless of ductility.

Whitish highly alkaline deposits or sparkling magnetite may indicate a corrosion sight.

To eliminate this problem either the stresses can be removed or the corrodent. The
stresses may be hoop stress( temp', pressure) which cannot be avoided bending or
residual weld stresses which must be removed in the design/ manufacturing stage.

Avoidance of the concentrations of the corrodents is generally the most successful. Avoid
DNB , avoid undue deposits prevent leakage of corrodents, prevent carryover.

Proper water treatment is essential.

Caustic corrosion

o Takes place at high pressure due to excessive NaOH

o In high temperature, high evaporation rates leading to local concentrations
nearly coming out of solution and form a thin film near heating surface.
o Magnetite layer broken down
o Soluble compound formed which deposits on metal as a porous oxide
o Local concentrations may cause a significant overall reduction in
alkalinity.
o If evaporation rate reduced alkalinity restored.

More in depth:

Generally confined to

1. Water cooled in regions of high heat flux

2. Slanted or horizontal tubes
3. Beneath heavy deposits
4. Adjacent to devices that disrupt flow ( e.g. backing rings)

Caustic ( or ductile ) gouging refers to the corrosive interaction of concentrated NaOH

with a metal to produce distinct hemispherical or elliptical depressions.

Depression are often filled with corrosion products that sometimes contain sparkling
crystals of magnetite.

Iron oxides being amphoteric are susceptible to corrosion by both high and low pH
enviroments.
High pH substances such as NaOH dissolve the magnetite then attack the iron.

The two factors required to cause caustic corrosion are;

o the availability of NaOH or of alkaline producing salts. ( e.g. intentional

by water treatment or unintentional by ion exchange resin regeneration.)
o Method of concentration, i.e. one of the following;
1. Departure form nucleate boiling (DNB)
2. Deposition
3. Evapouration

i)Departure form nucleate boiling (DNB)

Under normal conditions steam bubbles are formed in discrete parts. Boiler water solids
develop near the surface . However on departure of the bubble rinsing water flows in and
redissolves the soluble solids

However at increased rates the rate of bubble formation may exceed the flow of rinsing
water , and at higher still rate, a stable film may occur with corrosion concentrations at
the edge of this blanket.
The magnetite layer is then attacked leading to metal loss.
The area under the film may be relatively intact.

ii), Deposition
A similar situation can occur beneath layers of heavy deposition where bubbles formation
occur but the corrosive residue is protected from the bulk water

iii), Evaporation at waterline

Where a waterline exists corrosives may concentrate at this point by evaporation and
corrosion occurs.

prevention's

 Rifling is sometimes fitted to prevent DNB by inducing water swirl.

 Reduce free NaOH by correct water treatment
 Prevent inadvertent release of NaOH into system (say from an ion exchange
column regenerator )
 Prevent leakage of alkaline salts via condenser
 Prevent DNB
 Prevent excessive waterside deposits
 Prevent creation of waterlines in tubes- slanted or horizontal tubes are particularly
susceptible to this at light loads were low water flows allow stm water
stratification.

Hydrogen attack
If the magnetite layer is broken down by corrosive action, high temperature hydrogen
atoms diffuse into the metal, combine with the carbon and form methane. Large CH-3
molecules causes internal stress and cracking along crystal boundaries and sharp sided
pits or cracks in tubes appear.

more in depth: Generally confined to internal surfaces of water carrying tubes that are
actively corroding. Usually occurs in regions of high heat flux, beneath heavy deposits, in
slanted and horizontal tubes and in heat regions at or adjacent to backing rings at welds or
near devices that disrupt flow .

Uncommon in boilers with a W.P.of less than 70 bar

A typical sequence would be ;

 NaOH removes the magnetite

 free hydrogen is formed ( hydrogen in its atomic rather than diatomic state) by
either the reaction of water with the iron reforming the magnetite or by NaOH
reacting with the iron
 This free hydrogen can diffuse into the steel where it combines at the grain
boundaries to form molecular hydrogen or reacts with the iron carbide to form
methane
 As neither molecular hydrogen or methane can diffuse through the steel the gasses
build up , increasing pressure and leading to failure at the grain boundaries
 These micro cracks accumulate reducing tensile stress and leading to a thick
walled failure. Sections may be blown out.
 This form of damage may also occur in regions of low pH
 For boilers operating above 70 bar , where high pH corrosion has occurred the
possibility of hydrogen damage should be considered

High temperature corrosion.

Loss of circulation , high temperature in steam atmosphere, or externally on suphtr tubes

Chelant corrosion

Concentrated chelants ( i,e. amines and other protecting chemicals) can attack magnetite ,
stm drum internals most susceptible.
A surface under attack is free of deposits and corrosion products , it may be very smooth
and coated with a glassy black like substance
Horse shoe shaped contours with comet tails in the direction of the flow may be present.

Alternately deep discrete isolated pits may occur depending on the flow and turbulence

The main concentrating mechanism is evaporation and hence DNB should be avoided

Careful watch on reserves and O2 prescience should be maintained

Low pH attack

Pure water contains equal amounts of hydrogen and hydroxyl ions . Impurities change the
balance . Acidic water has an excess of hydrogen ions which leads to hydrogen
evolution.See previous notes on Hydrogen Evolution

For hydrogen absorption to occur no oxygen needs to be present, a pH of less than 6.5
and so an excess of free hydrogen ions is required.
The Protective film of hydrogen gas on the cathodic surface breaks down as the hydrogen
combines and bubbles off as diatomic hydrogen gas.
May occur due to heavy salt water contamination or by acids leaching into the system
from a demineralisation regeneration.

Localised attack may occur however where evaporation causes the concentration of acid
forming salts . The mechanism are the same as for caustic attack. The corrosion is of a
similar appearance to caustic gouging

Prevention is the same as for caustic attack . Proper maintenance of boiler water
chemicals is essential

Vigorous acid attack may occur following chemical cleaning . Distinguished from other
forms of pitting by its being found on all exposed areas
Very careful monitoring whilst chemical cleaning with the temperature being maintained
below the inhibitor breakdown point. Constant testing of dissolved iron and non ferrous
content in the cleaning solution should be carried out.

After acid cleaning a chelating agent such as phosphoric acid as sometimes used . This
helps to prevent surface rusting , The boiler is then flushed with warm water until a
neutral solution is obtained.

Oxygen corrosion

Uncommon in operating boilers but may be found in idle boilers.

Entire boiler susceptible , but most common in the superheater tubes (reheater tubes
especially where water accumulates in bends and sags )

In an operating boiler firstly the economiser and feed heater are effected.

In the event of severe contamination of oxygen areas such as the stm drum water line and
the stm separation equipment

In all cases considerable damage can occur even if the period of oxygen contamination is
short

Bare steel coming into contact with oxygenated water will tend to form magnetite with a
sound chemical water treatment program.
However , in areas where water may accumulate then any trace oxygen is dissolved into
the water and corrosion by oxygen absorption occurs( see previous explanation )

Oxygen Absorption

in addition to notes above pH between 6- 10, Oxygen present.

Leads to pitting. Very troublesome and can be due to ineffective feed treatment prevalent
in idle boilers. Once started this type of corrosion cannot be stopped until the rust scab is
removed , either by mechanical means or by acid cleaning.

One special type is called pitting were metal below deposits being deprived of oxygen
become anodic . More common in horizontal than vertical tubing and often associated
with condensers.

The ensuing pitting not only causes trouble due to the material loss but also acts as a
stress raiser

The three critical factors are

1. the prescience of water or moisture

2. prescience of dissolved oxygen
3. unprotected metal surface

The corrosiveness of the water increases with temperature and dissolved solids and
decreases with increased pH
Aggressiveness generally increases with increased O2

The three causes of unprotected metal surfaces are

1. following acid cleaning

2. surface covered by a marginally or non protective iron oxide such as
Hematite (Fe2O3)
3. The metal surface is covered with a protective iron oxide such as
magnetite (Fe3O4 , black) But holidays or cracks exist in the coating, this
may be due to mechanical or thermal stressing.

During normal operation the environment favours rapid repair of these cracks. However,
with high O2 prescience then corrosion may commence before the crack is adequately
repaired.

FEED SYSTEM CORROSION.

Graphitization

Cast iron , ferrous materials corrode leaving a soft matrix structur of carbon flakes
Dezincification

Brass with a high zinc content in contact with sea water , corrodes and the copper is
redeposited. Inhibitors such as arsenic , antimony or phosphorus can be used , but are
ineffective at higher temperatures.
Tin has some improving effects

Exfoliation (denickelfication)

Normally occurs in feed heaters with a cupro-nickel tubing ( temp 205oC or higher)
Very low sea water flow condensers also susceptible.
Nickel oxidised forming layers of copper and nickel oxide

Ammonium corrosion

Ammonium formed by the decompositin of hydrazine

Dissolve cupric oxide formed on copper or copper alloy tubes
Does not attack copper, hence oxygen required to provide corrosion,Hence only possibel
at the lower temperature regions where the hydrazine is less effective or inactive,
The copper travels to the boiler and leads to piting.

Deposits and scales found in boilers

Definition: material originating elsewhere and conveyed to deposition site; Oxides
formed at the site are not deposits.

Water formed and steam formed deposits

o May occur anywhere

o Wall and screen tubes most heavily fouled , superhtr has deposits formed
elsewhere and carried with the steam or carryover. Economisers ( non-
steaming) contain deposits moved from there original site.
o Tube orientation can influence location and amount of deposition.
o Deposits usually heaviest on the hot side of the steam generating tubes.
Because of steam channelling, deposition is often heavier on the top
portion of horizontal or slanting tubes
o Deposition occurs immediately downstream of horizontal backing rings.
o Water and steam drums can contain deposits, as these are readily accessed
then inspection of the deposition can indicate types of corrosion. e.g.
Sparkling black magnetite can precipitate in stm drums when iron is
released by decomposition of organic complexing agents.
o Superhtr deposits ( normally associated with high water levels and
foaming ) tend to concentrate near the inlet header or in nearby pendant U-
tubes
 o Contaminated attemperating spray water leads to deposits immediately
down stream with the possibility of chip scale carried to the turbines.
o At high heat transfer rates a stable thin film boiling can occur, the surface
is not washed ( as it is during bubble formation ) and deposits may form
o Thermal stressing can lead to oxide spalling ( the exfoliation of oxide
layers in areas such as the suphtr). These chips can pass on to the turbine
with severe results. Steam soluble forms can be deposited on the turbine
blades , If chlorides and sulphates are present , Hydration can cause severe
corrosion due to hydrolysis.
o As deposits form on the inside of waterwall the temperature increases.
This leads to steam blanketing which in turn leads to reduced heat transfer
rate , long term overheating and tube failure.

Effects on tube temperature of scale deposit

DEPOSITS

Iron oxides

Magnetite (Fe3O4)
A smooth black tenacious , dense magnetite layer normally grows on boiler water side
surfaces.taken to indicate good corrosion protection as it forms in low oxygen levels and
is susceptible to acidic attack

Heamatite (Fe2O3)
is favoured at low temperatures and high oxygen levels can be red and is a binding agent
and tends to hold over materials in deposition. This is an indication of active corrosion
occuring within the boiler/feed system
Other metals

Copper and Copper oxide is deposited by direct exchange with iron or by reduction of
copper oxide by hydrogen evolved during corrosion . Reddish stains of copper are
common at or near areas of caustic corrosion. Copper Oxide appears as a black depositi.
It is considered very serious corrosion risk because of the initiation of galvanic corrosion
mechanisms.

Galvanic corrosion associated with copper deposition is very rare in a well passivated
boiler. Zinc and nickel are very often found near copper deposition , nickel being a
particularly tenacious binder

Rapid loss of boiler metals can occur. Copper can appear in various forms as a deposit in
the boiler. As a copper coloured metallic deposit, usually in a corrosion pit, as a bright
red/orange tubercules on the boiler metal surface or as a brown tear drop shaped
formation.

Copper is generally an indicator of corrosion (or possible wear) occuring in the feed
pump whether in the condensate lines or in the parts of a feed pump. A possoble cause of
this is the excessive treatement of hydrazine which decompose to ammonia carrying over
with the steam to attack suc areas as the air ejectors on condensers.

Copper oxide formed in boiler conditions is black and non- metallic.

SALTS

The least soluble salts deposit first

Calcium carbonate-effervesces when exposed to HCl acid

Calcium sulphate-Slightly less friable then CaCO3

Magnesium Phosphate-Tenacious binder, discoloured by contaminants

Silicates-Insoluble except in hydroflouric acid E.G. Analcite

Water soluble deposits can only be retained if local concentration mechanism is severe.
Prescence of NaOH , NaPO3 Na2SO3 should be considered proof of vapouration to
dryness.

Calcium and magnessium salts exhibit inverse solubility. As the water temperature rises
their solubility reduces, at a temperature of 70'C and above they come out of solution and
begin to deposit. Feed water must be condition to remove the hardness salts before the
water enters the boiler. The purity of the water is related to the steam conditions required
of the boiler.
Hydrolyzable salts such as MgCl can concentrate in porous deposits and hydrolyze to
hydrochloric acid

Scaling mechanism examples

Calcium Carbonate
Cacium Carbonate is formed by the thermal decomposition of Calcium BiCarbonate and
apperas as a pale cream to yellow scale

Ca(HCO3)2 + Heat = CaCO3 + H2O + CO2

Magnessium Silicate
Tor form requires sufficient amounts of magnessium and silicate ions coupled with a
deficiency in OH- alkalinity

Mg2+ + OH- = MgOH+

H2SiO3 = H+ + HSiO3-

MgOH- + HSiO3- = MgSiO3 + H2SO4

Thus this rough tan scale can be prevented by the maintenace of alkalinity levels

Calcium Phosphate (hydroxyapatite)

Ca10(PO4)6(OH)2
Found in biolers using the phosphate cycle treatment method this is a tan/cream deposit.
This is generally associated with overdosing a boiler but can occur where insufficient
disperseing agent reduces the effects of blow down.

In anouther form Ca3(PO4)2Ca(OH)2 it is associated with correct treatment control

Scales forming salts found in the boiler

Calcium Bi-Carbonate 180ppm

o Slightly soluble
o >65oC breaks down to form CaCO3 +CO2, remaining Calcium carbonate
insoluble in water
o Forms a soft white scale

Magnesium BiCarbonate 150 ppm

o Soluble in water
o at more than 90oC breaks down to form MgCO3 and CO2 and then
Mg(OH)2 and CO2
o Forms a soft scale

Calcium Sulphate 1200 ppm

o Worst scale forming salt

o > 140oC (sat. press 2.5bar) or >96000ppm will precipitate out
o Forms a thin hard grey scale

Magnesium Sulphate 1900ppm

o Precipitates at high temperatures and about 8 bar

o Forms sludge

Magnesium Chloride 3200ppm

o Breaks down in boiler conditions to form MgOH and HCl

o forms a soft white scale Rapidly lowers pH in the event of sea water
contamination of the boiler initiating rapid corrosion MgCl2 + 2H2O--->
Mg(OH)2 + 2HCl HCl + Fe --->FeCl + H 2FeCl + Mg(OH)2 ---> MgCl2
+ 2FeOH This series is then repeated. Effective feed treatment ensuring
alkaline conditions controls this problem

Sodium Chloride 32230 to 25600 ppm

o Soluble <225000ppm
o forms a soft encrustation
 o Free irons promote galvanic action

Other deposits-

Amorphous Silicon dioxide (SiO2) - trace

o at high tempos and pressures (>40bar) silica can distill from the bioler as
Silicic acid and can sublime and pass over into the steam system as a gas.
Here it glazes surfaces with a smooth layer, which due to thermal
expansion crack and roughen the surface. Troublesome on HP blading.
Can be removed only by washing with Hydroflouric acid.

Magnessium Silicate 3MgO.2SiO2.2H2O (Serpentine) is formed in water

with proper treatment control

SCALE FORMATION

The roughness of the heated surface has a direct relationship to the deposit of scale. Each
peak acts as a 'seed' for the scale to bind to.

Nucleate Boiling

Scale built up as a series of rings forming multi layers of different combinations. Much
increased by corrosion products or prescience of oil, even in very small quantities.
Oil also increases scale insulatory properties.

Departure form nucleate boiling (DNB) Under normal conditions steam bubbles are
formed in discrete parts. Boiler water solids develop near the surface . However on
departure of the bubble rinsing water flows in and redissolves the soluble solids
However at increased rates the rate of bubble formation may exceed the flow of rinsing
water , and at higher still rate, a stable film may occur with corrosion concentrations at
the edge of this blanket.

Dissolved solids in fresh water

Hard water -Calcium and magnesium salts

- Alkaline
-Scale forming
.
.
Soft water -Mainly sodium salts
- Acidic
- Causes corrosion rather than scale

Boiler water tests

Corrosion and tube failure caused by water chemistry

Recommended ranges( Co-ordinated phosphate treatment for w/t boiler )

pH - 9.6 to 10.3
PO4 - 4 to 20 ppm
N2H4 - 0.01 to 0.03 ppm
TDS - < 150 ppm
Cond pH - 8.6 to 9.0
Cl - 20 ppm
O2 - 10 ppb
Si - 10 ppb

Chlorides

o Measure 100ml of sample water into a casserole

o Add 10 drops phenol pthalein (RE 106)
o Neutralize with sulphuric acid
o Add 10 drops of Potassium Chromate
o Titrate Silver Nitrate untill sample just turns brick red
o ppm as CaCO3= (ml x 10) ppm

TDS
 o Measure 100ml of sample water into a casserole
o Add 10 drops of phenolpthalein
o Neutralise with TDS reagent (acetic acid)
o Temperature compensate then read off scale in ppm.

Phosphates

o Fill one 10 ml tube with distilled water

o Fill one 10 ml tube with boiler water tests.
o Add 0.5 ml sulphuric acid (RE 131) to each
Add 0.5 ml Ammonium Molybdnate (RE130) to each
Add 0.5 ml Aminonapthol Sulfonic acid (RE 132) to each
Stir well between each addition
o Wait 3 minutes for calorimetric compaison

Alternately Vanado-molybdnate test

o Place 5 ml boiler water in 10 ml tube

o Place 5 ml distilled water in other 10 ml tube
o Top both to 10 ml with Vanado-molybdnate reagent
o Place in colour comparator and compare after 5 mins

Hydrazine

o Add 9ml distilled water to one tube

o Add 9 ml boiler test water to anouther
o Add 1 ml hydrazine reagent to each
o Use colour comparator

Alkalinity Phenolpthalein

o 100 ml filtered water

o Add 1 ml phenolpthalein
o If pH >8.4 Solution turns pink
o Add H2SO4 untill pink disapears
o Ml 0.02N H2SO4 x 10 = ALk in CaCO3 ppm
o Measures hydroxides and carbonates in sample, bi-carbonates do not show
up so sample should not be allowed to be exposed to the air for too long

Alkalinity Methyl orange

Bi carbonates do not show up in the phenolpthalein sample as they have a

pH < 8.4. Bi carbonates can not occur in boiler but if suspected in raw
feed then the following test.

o Take phenolpthalein sample, add 1 ml methyl orange

 o If yellow, bi carbonates are present
o Add H2SO4 untill red
o Total 0.02N H2SO4 x 10 = Total Alk in CaCO3

pH

o 100 ml unfiltered sealed water poured into two 50 ml glass stoppered test
tubes
o Add 0.2 ml pH indicator to one ( pH indicator vary's according to required
measuring range)
o Use colour comparator
o Due to difficulty of excluding air, electronic pH meter preferred

Sulphite reserve

o Exclude air at all stages

o 100 ml unfiltered water
o Add 4 ml H2SO4 + 1 ml starch
o Add potassium iodate-iodide untill blue colour
o ml Iodate-Iodide sol x 806 / ml of sample = SO3 reserve in ppm

Ammonia in feed

o Only necessary where N2H4 used in blr

o Pour condensate sample into two 50 ml colour comparator tubes
o Add 2 ml Nessler reagent to one
o Wait 10 mins
o Use colour comparator

Boiler water treatment

Alkalinity
Treatment

For pressures below 20 bar dissolved O2 in the feed does not cause any serious problems
so long as the water is kept alkaline
However cold feed should be avoided as this introduces large amounts of dissolved O2
are present, for pressures greater than 18.5 bar a dearator is recommended

Feed Treatment Chemicals

Sodium Hydroxide
Calcium Bicarbonate (CaCO3 + Na2CO3)
Magnesium Bicarbonate
Magnesium Chloride.
. .
Sodium Phosphate
Calcium Carbonate
Calcium Sulphate
Magnesium Sulphate
All in this column precipitated as
All in this column form sodium
hydroxide or phosphate based
salts which remain in solution
sludges

 Sodium Hydroxide
o Reacts with highly corrosive MgCl2
o Does not readily react with CaSO4
 o Strongly alkaline
o Produces heat when mixed with water
o Absorbs CO2 changing to Sodium Carbonate
o Unsuitable for standard mixes

 Sodium Carbonate Na2CO3 ( soda ash )

o Alkaline
o At pressures above 14 bar some of the Sodium Carbonate decomposes to
form NaOH and CO2 . Increasing on pressure increase
o Changes to Sodium Bi-Carbonate when exposed to air
o Still usable but larger amounts make control difficult
o Standard mix ingredient

 Sodium Hexa Meta Phosphate NaPO3 (calgon)

o Safe,soluble in water, slightly acidic
o May be injected any where as will only react in the boiler
o Suitable for LP blrs which require lower alkalinity

 DiSodium Phosphate Na2HPO4 (Cophos II)

o Neutral used with alkaline additive
o Combines with NaOH to give trisodium phosphate
o Basic constituent

 TriSodium Phosphate Na3 PO4 (Cophos III)

o Alkaline
o When added to water decomposes to NaOH and Na2 HPO4
o As water evaporated density increases and NaOH and Na2 HPO4
recombine
o Phosphates can form Phosphides which can coat metal to form a
protective barrier, with excessive phosphate levels, this coating can be
excessive on highly rated boilers operating at higher steaming rates

Chemicals are normally added as a dilute solution fed by a proportioning pump or by

injection from pressure pot.
Use of chemicals should be kept to a minimum.

Injection over a long period is preferable as this prevents foaming.

Excessive use of phosphates without blowdown can produce deposits of phosphides on a

par with scale formations.

Therefore it is necessary to add sludge conditioners particularly in the forms of

polyelectrolytes, particularly in LP blrs

Oxygen Scavengers
 Hydrazine N 2 H 4
o Oxygen scavenger, continously injected to maintain a reserve within the
boiler of 0.02 to 0.1 ppm and a feed water O2 content of less than 10 ppb
o At temperatures greater than 350oC , will decompose to ammonia and
nitrogen and will aid in maintaining balanced alkalinity in steam
piping.Steam volatile, neutralises CO2
o Inherent alkalinity helps maintain feed water alkalinity within parameters
of 8.6 to 9.0.
o Used in boiler operating above 32 bar, will not readily react with O2 below
50oC hence risk of copper corrosion occurs with the ammonia stripping off
the continuously reforming copper oxides.
o Supplied as a 35% solution

 Carbohydrazide (N 2 H3)2CO
o Is a combined form of Hydrazine
o It is superior to hydrazine in performace and is designed to minimise the
vapours during handling
o Carbohydrazide and its reaction products create no dissolved solids
o Is an oxygen scavenger and metal passivator at both high (230'C) and low
(65'C) temperatures
o Can be used with boilers up to 170 bar

 Diethylhydroxylamine DEHA
o Like hydrazine, provides a passive oxide film ( magnetite) on metal
surfaces to minimise corrosion
o Contributes to pH netralisation to an extent that seperate condensate
control may not be necessary
o Protects entire system-feedwater, boiler and condensate

 Sodium sulphite Na2SO3

o Takes the form of a soft white powder
o Slightly alkaline
o Will react with oxygen to form Sodium Sulphate at about 8ppm Sodium
Sulphite to 1ppm Oxygen
o Use limited to low pressure boilers due to increasing TDS and reducing
alkalinity by its action

 Tannins
o Certain alkaline tannin solutions have a good oxygen absorbing ability
with about 6ppm tannin able to remove 1ppm oxygen.
o The reaction with oxygen is complex and unreliable, no official reserve
levels exist for the maintenance of a system using tannin

 Erythorbic Acid (Sur-gard) R1-C(OH)

o An effective oxygen scavenger and metal passivator
 o It is the only non-volatile scavenger which can be used with spray
attemperation
o does not add measureable solids to the boiler water
o May be used in boilers up to 122 bar
o Officially recognised as a Safe Substance
o As with hydrazine a small amount of ammonia is created in the boiler, it is
not recommended for layup.

Polymer Treatment

Polymer is a giant molecular built up by stringing together simple molecules

E.G.
Polyelectrolytes-Formed from natural or synthetic ionic monomers
Polyacrylates - Polymers of acrylic acid
Polyamides - Polymers of amides

Polymer treatment prevents scale formation and minimises sludge formation. It can also
loosen scale so established blrs introduced to this form of treatment may develop leaks
where previously plugged with scale. Especially in way of expanded joints. Also can
absorb trace oil

Use limited to LP blrs as no PO4 present to prevent caustic alkalinity

For auxiliary blrs this is a superior form of treatment to the old alkaline and phosphate
treatment. The correct level of alkalinity must be maintained as too low a level
neutralises the electric charge of the polyelectrolyte. Too high causes caustic alkalinity.

Amine treatment

Compounds containing nitrogen and hydrogen.

Neutralising amines

Hydrazine N2H4

see above

Bramine ( cyclohexalamine )

(Bull & Roberts amine treatment)

Neutralising amine as with hydrazine. Used with hydrazine to maintain feed water
alkalinity within parameters. As a knock on effect will slightly increase boiler water
alkalinity.
Stable at high temperatures so is used more than hydrazine to control the steam line
alkalinity as there is less chance of copper corrosion which occurs with the prescience of
ammonia

Proper boiler water treatment eliminates sludge and scale deposits within the boiler.
However, over along period of time a film of copper and iron oxides build up on the tube
surface. Most of these oxides are transported from oxides of corrosion within the feed
system to the boiler with the condensate.

Bramine reduces this corrosion and eliminates the build up of these oxide deposits.

Mechanism of function
Condensate from the condenser is very pure and slightly acidic, often referred to as
'hungry water'. It can dissolve metals in trace amounts to satisfy this hunger.
Distilled make up water aggravates this situation containing much dissolved CO2 and
hence being acidic carries its own corrosion products.
Trace amounts of bramine are introduced into the system to establish an alkalinity level
greatly reducing the effects of the hungry water.

Some of the bramine is used almost immediately, most however, passes on to the boiler
where it is then transported through boiler water, boiler stm drum, stm lines back to the
condenser. It has no effect anywhere except the condensate system.

Bramine also has a cleaning effect and may assist in the cleaning the film off the tube
over a period of time.
Bramine is safer to handle than Bramine and will protect all metals.

Hydrazine however readily breaks down to form ammonia which whilst protecting
ferrous metals will attack those containing copper

Filming amines

Shows neutralising tendencies, main function however is to coat piping with a molecular
water repellent protective film

Injection of amines
May be injected between HP and LP turbines in the X-over pipe or after the dearator.
Adding in X-over pipe-reduces corrosion of copper alloys
Dearator only effective as a feed heater

Adding after dearator -Dearator correctly performing as a dearator and feed heater. If
possible the best system is to have a changeover to allow norm inj into the X-over at sea
and injection after the dearator when the turbine shut down

Limits of density/pressure
Sludge conditioning agents

 Coagulants-
o Mainly polyelectrolytes
o Prevents the precipitated sodium based particles forming soft scales
o Will keep oil in an emulsion
o the water must be kept alkaline

 Antifoams
o reduce the stability of water film around steam bubble and cause it to
collapse.
o Common type polyamide is an organic compound of high molecular
weight.
o In the event of severe contamination separate injection of an antifoam is
recommended

 Dispersing agents
o Sludge conditioners such as starch or tannin.
o Prevent solid precipitates uniting to form sizeable crystals e.g. MgSO4

Treatment in boilers (non congruent)

LP tank blrs (<14 bar)

Na2CO3- precipitates salts, provides alkalinity

MgSO4- Sludge conditioners
Na2CO3 can break down to form NaOH in higher rated boilers hence initial dose with
Na2SO4

Medium pressure tank blrs (<17.5 bar)

Na2CO3(3) + sodium phosphate(4) + sludge conditioners(1)

Medium to High pressure water tube <60 bar

Na2CO3 + Na2HPO4 +sludge conditioners

Oxygen scavengers also used to allow magnetite (Fe3O4) layer to form in the boiler

Boiler operating above 42 bar require a dearator.

HP to UHP blrs (42 to 80 bar)

Due to level of decomposition of Na2CO3 . NaOH preferred for better controllability

Na2HPO4

NaOH attacks the magnetite layer. Congruent treatment used.

Permissible limits

Shell WT WT WT WT WT
TEST> PPM <17.5b <17,5b <32b <42b <60b <85b
Hardness CaCO3 <=5 <=5 <=5 <=1 <=1 <=1
P.alk CaCO3 150-300 150-300 150-300 100-150 50-100 50-80
T.D.S. CaCO3 <=7000 <=1000 <=1000 <=500 <=500 <=300
Cl CaCO3 <=1000 <=300 <=150 <=100 <=50 <=30
PO4 PO4 30-70 30-70 30-70 30-50 30-50 20-30
N2H4 N2H4 -- -- -- 0.1 -1.0 0.1 - 1.0 0.1 - 1.0
SO3 SO3 50-100 50-100 50-100 20-50 -- --
SiO2 SiO2 -- -- -- -- -- <=6.0
Fe Fe -- -- -- -- -- <=0.05
Cu Cu -- -- -- -- -- <=0.02
pH pH 10.5-11 10.5-11 10.5-11 10.5-11 10.5-11 10.3-11
Limits for feed water
Cl CL <=10 <=5 <=1.0 <=1.0 <=1.0 <=1.0
O2 O2 ---- ---- <=0.006 <=0.003 <=0.015 <=0.01
NH3 NH3 ---- ---- ---- ----- ----- <=0.5
Fe Fe ---- ---- ---- ----- <=0.01 <=0.01
Cu Cu ---- ---- ---- ----- <=0.01 <=0.01
pH pH ---- ---- ---- 8.5-

Co-ordinated and congruent Phosphate

treatmentst
Alkalinity

NaOH under certain conditions dissolves boiler metal.

Co-ordinated treatment tries to avoid this by relying on the fact that NaOH and disodium
phosphate combine to form trisodium phosphate. However, a small proportion of the
NaOH always remains. Congruent treatment tries to avoid this by making a mix so that
the Na+ to PO-34 ion ratio never exceeds 2.6 : 1 ( Na3PO4 has a sodium to phosphate ratio
of 3 : 1 )

Co-ordinated phosphate treatment

 Purpose
o to maintain a phosphate reserve to react with incoming hardness
o To maintain sufficient alkalinity to minimise corrosion and aid in forcing
the reaction with hardness salts.

For boiler pressures above 40bar problems of caustic alkalinity caused by addition of
caustic soda as part of a feed treatment occur.
With caustic alkalinity, free hydroxides concentration in a thin film at the tube surface
destroying the protective magnetite layer and attacking the metal to form caustic gouging
craters, and intercrystaline cracking as it attacks the iron carbide in the iron grain
boundaries.
Avoiding the prescience of free hydrides is the only prevention from this form of attack

Co-ordinated phosphate-pH control

Maintaining within the control area is achieved by the addition of Co-phos III tri sodium
phosphate based, and co-phos II, disodium phosphate based.

Co-Phos III is an alkaline product and in water decomposes to NaOH and Na2HPO4
increasing concentration recombine.

Co-Phos II is much less alkaline.

Falling into the area on the co-ordinated phosphate pH diagram below the lower dotted
line means that normal treatment to bring back into the target area is impossible.

The only way of recovering the situation is by blowing large quantities of water out of the
boiler

The ideal time for this is during trip testing when the boiler is isolated from the plant (and
hence feed water flow to the boiler is much reduced). The flames are extinguished on the
low low foxboro trip

It is also beneficial to blow down the headers at this time

Problems may arise when the mixed bed demineralisation plant is allowed to remain in
need of regeneration for a long time. The make up water is so effected so as to lower the
alkalinity of the boiler without a comparable drop in phosphate. This becomes
particularly troublesome during periods of heavy make up, say during trip testing or
heavy steaming.

Hide-out

It can be seen in high pressure boilers that as the steaming rate increases the levels of
certain salts, particularly phosphate salts, does not raise in line with others. When the
load is reduced the concentrations return to normal.

This is termed hide-out and is due to the reduced solubility of sodium phsophate at
temperatures above 250'C

When phosphate hide-out occurs there is a risk of permenant scal deposition and/or
evolution of free caustic which in turn could lead to severe corrosion due to caustic attack

Treatment using volatile solids free chemicals such as hydrazine, Eliminox and
neutralising amines should be considered. This is termed All Volatile Treatment (AVT)

Theory of Feed Heating

The purpose of feed heating is to increase plant efficiency. With no feed heating steam
gives up three times more heat to the cooling water as it does in doing useful work in the
turbine. Hence, if a proportion of the steam is bled off to a feed heater it can give energy (
its latent heat mostly) to the feed and so a higher proportion of the energy is reclaimed by
the system as would have been gained by expanding it through the turbine to the
condenser Feed heating can take two forms, one is contact heating which occurs in the
Deaerator where the steam and feed water mix and and the water directly receives heat.

Theoretical cycle with all steam expanded through the turbine

Theoretical cycle where all of the steam used in feed heating with 100%
efficiency

This could only be possible where the turbines where fitted with a water jacket through
which the feed water flows.

Theoretical practical cycle where a portion of the steam is bled off in

stages and used for feed heating
It should be noted that although thermal efficiency increases with the number of stages, it
is governed by the law of diminishing returns and the improvement is reduces with
successive stages. Hence the cost of the increased plant becomes a factor.

Bleeding off a portion of the steam gives the added advantage that the steam volume that
has to be accommodated in the final stages of the turbine and condenser is reduced.